Metallized anthraquinone dyes



M atent iee METALLIZED ANTHRAQUINONE DYEs James M. Straley and David G. Hedberg, Jr., Kingsport,

Tenn, assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey N Drawing. Application March 7, 1958 Serial No. 719,756

20 Claims. (Cl. 260-366) This invention relates to new metallized anthraquinone compounds and their application to the art of dyeing or coloring. Insofar as dyeing is concerned the invention is particularly directed to the dyeing of cellulose acetate textile materials.

The metallized anthraquinone compounds of our invention comprise the anthraquinone compounds having the formula:

wherein R represents a monocyclic aryl nucleus of the benzene series and X and Y each represent a different member selected from the group consisting of a hydroxy group and a nitro group in complex combination with chromium, cobalt, copper, iron, manganese, nickel or vanadium.

The anthraquinone compounds having the formula:

HO O OH wherein R represents a monocyclic aryl nucleus of the benzene series are prepared by reacting 1,8-dihydroxy- 4,5-dinitroanthraquinone with a primary amine having the formula RNH wherein R has the meaning just given.

Similarly, the anthraquinone compounds having the formula:

O N fl) (I)H 0 I HO B T-R H III wherein R represents a monocyclic aryl nucleus of the benzene series are prepared by reacting 1,5-dihydroxy- 4,8-dinitroanthraquinone with a primary amine having the formula RNH wherein R has the meaning just given. The manner of preparing the anthraquinone compounds having the formulas numbered II and III is apparent from US Patents 2,053,274; 2,480,269; 2,641,602; 2,651,- 641; 2,713,060; 2,726,251; 2,777,883 and 2,798,081 which illustrate the general reaction involved and which disclose numerous compounds embraced by said Formulas II and III.

As is well known, one of the disadvantages dyed cellulose acetate textile fabrics suffer in comparison with some of the dyed competing textile fabrics, such as cotton, wool and viscose, for example, is lack of fastness to washing. Many schemes have been proposed to remedy this situation but all suffer from some significant fault. By means of our invention dyed cellulose acetate textile materials having good to excellent fastness to washing, light, gas and sublimation are obtainable. These results may be obtained by dyeing the cellulose acetate textile material with the non-metallized anthraquinone compounds having the Formulas II and III and then treating the dyed cellulose acetate textile material with suitable metal salts which cause the original dye to form metallic com"- plexes which are resistant, for example, to the action of washing, light, gas and sublimation. Thus, by means of the present invention, the disadvantage noted above with respect to the wash fastness of dyed cellulose acetate textile materials is either entirely or largely overcome.

While reference has been made to the dyeing of cellulose acetate textile materials, it is to be understood that the invention is generally applicable to the dyeing of textile materials made of or containing a cellulose alkyl carboxylic acid ester having two to four carbon atoms in the acid groups thereof. By cellulose alkyl carboxylic acid esters having two to four carbon atoms in the acid groups thereof, we mean to include, for example, both hydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-propionate and cellulose acetate-butyrate. Cellulose acetate has been particularly referred to because it is the most widely used cellulose alkyl carboxylic acid ester.

The metallized anthraquinone compounds of our invention are prepared by treating the corresponding nonmetallized anthraquinone compounds having the Formulas II and III with salts of nickel, cobalt, copper, chromium, manganese, iron or vanadium. The nonmetallized anthraquinone compounds can be metallized either on or off the fiber. out, for example, by treating the non-metallized dye with a solution or dispersion of the metallizing agent. Although the metal complex of the dye is often formed at room temperature, we prefer to accelerate the process by heating, usually with steam, for a short time. The preparation of the metallized anthraquinone compounds of our invention is fully described hereinafter.

The non-metallized anthraquinone compounds having the Formulas II and III have varying utility for the dyeing of cellulose alkyl carboxylic acid esters having two to four carbon atoms in the acid groups thereof, nylon, acrylonitrile polymers, such as polyacrylonitrile and acrylonitrile graft polymers and polyesters, such as polyethylene terephthalate. After application to these materials, usually in the form of textile materials, the dye may be metallized thereon if desired. The metallized anthraquinone compounds of our invention can be applied by ordinary dyeing or printing techniques to nitrogenous textile materials such as wool, silk, nylon and acrylonitrile polymers such as polyacrylonitrile and acrylonitrile graft polymers. Coloration can also be effected by incorporating the non-metallized or metallized anthraquinone compounds into the spinning dope, spinning the fiber as usual and converting the non-metal1ized anthraquinone compounds to their metallized form if desired. Also, the metallizing agent can be incorporated in the spinning dope, the fiber spun as usual and then dyed with the non-metallized anthraquinone compounds to form the metal complex on the fiber. The metallized dyeings are frequently faster to light than the corresponding non-metallized dyeings.

Both the non-metallized and metallized anthraquinone compounds described herein are dyes for fibers prepared from graft polymers obtained by graft polymerizing acrylonitrile alone or together with one or more other Metallization can be carried.

monoethylenic monomers with a preformed polymer. The preformed polymer can be a homopolymer (a polymer prepared by polymerization of a single monomer) or it can be an interpolymer such as a copolymer a polymer prepared by the simultaneous polymerization m a single reaction mixture of two monomers) or a terpolymer (a polymer prepared by the simultaneous polymenzation in a single reaction mixture of three monomers), or the like, and the graft polymers for which the dyes are particularly useful are those containing at least by weight of combined acrylonitrile grafted to the preformed polymer molecule.

The graft polymers which can be dyed using the nonmetallized and metallized dyes are thus polymers having directed placement of the polymerized monomeric units in the graft polymer molecule as distinguished from the random distribution obtained in interpolymers which are prepared by simultaneous polymerization of all of the monomeric materials in the polymer. The preformed polymer can be either a homopolymer of any of the well-known polymerizable monomers containing a single CH=C group and desirably a CH =C group, or an interpolymer of two or more of such monomers; and the grafting can be eifected with the preformed homopolymer or interpolymer in the polymerization mixture in which it was formed (i.e. a dead polymer).

The preformed polymer desirably is a homopolymer of a vinyl pyridine, an acrylamide, a maleamide, a fumaramide, an acrylate, a methacrylamide, a methacrylate, an itaconamide, a citraconamide, a fumaramate, an itaconamate, a citraconamate, a maleamate, or a vinyl ester; or an interpolymer of two or more of such monomers with each other or of at least one of such monomers with one or more different monoethylenic monomers characterized by a -CH=C group such as styrene, acrylonitrile, substituted styrenes, vinyl or vinylidene chlorides, vinyl ethers, dialkyl maleatcs, alkenyl ketones, dialkyl fumarates, acrylic acid, methacrylic acid, substituted acrylonitriles, fumaronitrile, ethylene and the like.

The graft polymerization is effected by polymerizing acrylonitrile or a mixture of acrylonitrile with any other monoethylenic monomer, including any of the monomers enumerated hereinabove, with the preformed live or dead homopolymer or interpolymer whereby the acrylonitrile alone or together with another grafting monomer is combined with the preformed polymer molecule to give a graft polymer containing from 5 to 95% by weight of combined acrylonitrile.

The anthraquinone compounds described herein are of particular utility for dyeing fibers prepared from a graft polymer obtained by graft polymerizing acrylonitrile and an acrylamide or methacrylamide with a preformed copolymer of acrylonitrile and the same or different acrylamide or methacrylamide.

US. Patent 2,620,324, issued December 2, 1952, U.S. Patent 2,649,434, issued August 18, 1953, and US. Patent 2,657,191, issued October 27, 1953, disclose other typical manganese chloride, manganous sulfate, manganese acetate, manganese thiocyanate [Mn(SCN) ferric chloride, ferric fluoride, ferrous acetate, ferrous thiocyanate [Fe(SCN) ferric thiocyanate [Fe(SCN) and vanadiurn tribromide, are illustrative of the metallizing agents that can be employed.

When the metal complex is formed on a cellulose alkyl carboxylic acid ester, such as cellulose acetate fiber, the use of a metal thiocyanate appears to be advantageous and is preferred. Nickel thiocyanate appears to be especially useful and particular claim is laid to its use. Next to nickel thiocyanate the use of cobalt thiocyanate is preferred.

The following examples in which parts are expressed by weight illustrate our invention:

EXAMPLE 1 that a pickup of 60100% (based on the weight of the dyed fabric) was obtained. The fabric was then dried at room temperature and aged in a steam chest at 5 p.s.i. for

20-30 minutes. The fabric was then scoured at 60 C.

graft polymers that can be dyed with the anthraquinone v compounds described herein.

Illustrative of the metallizing agents that can be employed are the halides, the sulfates, the acetates, the

cyanides and the thiocyanates of nickel, cobalt, chromium, manganese, iron and vanadium as well as various copper compounds. Thus, nickel chloride, nickel bromide, nickel sulfate, nickel acetate, nickel cyanide, nickel formate, nickel thiocyanate [Ni(SCN) cobaltous bromide, cobaltic chloride, cobaltous chloride, cobaltous acetate, cobaltous cyanide, cobalt thiocyanate cupric chloride, cupric bromide, cupric acetate, cupric lactate, chromium trichloride, chromium tribromide, chromic sulfate, chromic acetate, chromium throcyanate.

[Cr (SCN) with soap and water, rinsed and dried. The cellulose acetate fabric resulting was a slightly greener blue than was the original non-metallized dyeing. change in depth of shade was noticed after a standard AATCC wash test at F. with soap and water. A slight break in color was noticed after 60 hours exposurein a Fade-Ometer.

EXAMPLE 2 A cellulose acetate fabric dyed as described in Example 1 was treated with a 2% aqueous solution of chromium thiocyanate instead of cobalt thiocyanate. The treatment was carried out exactly as described in Example 1. The metallized dyeing resulting has the same excellent wash and light fastness properties as the dyed fabric of Example 1.

EXAMPLE 3 A bright cellulose acetate-viscose check (50:50) was dyed in known manner using an aqueous dye bath prepared by using 2% by weight (based on the weight of the cellulose acetate) of a dye mixture containing 40% by weight of the blue dye 1,8-dihydroxy-4-(m-methylolanilino) -5-nitroanthraquinone and 60% by weight of sodium lignin sulfonate. After dyeing, the cellulose acetate-viscose fabric was dried and then padded with a 2% aqueous solution of nickel thiocyanate in such a manner that a pickup of 60-100% (based on the weight of the fabric) was obtained. The fabric was then aged in a steam chest at 5 p.s.i., scoured at 60 C. with soap and water, rinsed and dried. The cellulose acetate was dyed a clear greenish blue while the viscose remained completely white. No bleeding or change in strength of the dyeing was noticed after a standard AATCC wash test at 160 F. with soap, water and 0.5% sodium carbonate. A slight break in color was noticed after 60 hours exposure in a Fade-Ometer.

EXAMPLE 4 A print paste was prepared as follows:

Two parts of a dye mixture containing 40% by weight of the blue dye 1,8-dihydroxy-4-(p-p-hydroxyethylanilinO)-5-nitr0anthraquin0ne and 60% by weight of sodiurn lignin sulfonate was pasted with 5 parts of hot water and 6 parts of glycerin. 30 parts of a 9% aqueous nickel thiocyanate solution were stirred in and the resulting After the dyeing opera No bleeding or mixture was then mixed with 55 parts of an 8% aqueous gum tragacanth solution.

When a homogeneous dispersion of the printing paste was obtained, a bright cellulose acetate taffeta was printed through a screen with the printing paste using three squeegee passes. The cellulose acetate taffeta print resulting was dried in air and then aged for 30 minutes in a steam chest at 5 p.s.i. The print was then scoured at 80 C. in an aqueous solution of 1% of Triton 720 (a polyethylene oxide condensate of an alkyl phenol) and 0.5% sodium carbonate. After the scouring treatment, the print was rinsed well with water and then dried. The result was a brilliant, deep greenish-blue pattern on a white ground. No bleeding or change in depth of color was noticed after a standard AATCC wash test at 160 F. using soap, water and 0.5 sodium carbonate.

EXAMPLE 5 To a mix of 110 parts of the blue dye 1,8-dihydroxy-4- (p-fl-hydroxyethylanilino)-5-nitroanthraquinone in 1000- parts of formamide at 60 C. there was added 60 parts of copper acetate monohydrate in finely powdered condition. The resulting solution was then raised to 120 C. and held 4 hours at l20l30 C. The dye mixture was then cooled to 90 C. and poured into 5000 parts of water. The suspension resulting was brought to the boil, filtered and the dyed product collected on the filter was washed with boiling water and dried at 110 C. 121 parts of metallized dye product were recovered as a powder which dissolves in acetone only slightly to a much greener solution than does the nonmetallized starting anthraquinone dye compound. When the metallized anthraquinone dyestutf is finely ground and intimately dispersed in a cellulose acetate-acetone dope and the dope is extruded into yarn in the usual manner, beautiful blue-green shades, much greener than obtained with the starting material, result.

EXAMPLE 6 A cellulose acetate yarn containing 1% of cupric bromide (the cupric bromide being added to the dope from which the yarn is spun) was dyed with 1% (based on the weight of the yarn) of the blue dye 1,8-dihydroxy- 4-anilino-S-nitroanthraquinone. After drying, the dyed cellulose acetate yarn was aged in a stream chest at 5 p.s.i. for 20 minutes. The yarn was dyed a greenishblue shade having excellent fastness to washing and. light.

EXAMPLE 7 A cellulose acetate fabric was dyed in known manner using an aqueous dye bath prepared by using 3% by weight of a dye mixture containing 40% by weight of theblue dye 1,8-dihydroxy-4-(m-methylolanilino)-5-nitroan-- thraquinone and 60% by weight of sodium lignin sulfonate. After drying, the fabric was padded with a solution of 6 parts Cuprofix (a mixture of copper sulfate and a low urea-formaldehyde polymer) in 200 parts of water and then dried. The padded cellulose acetate fabric was then cured at 160 C. for 5 minutes and then scoured at 60 C. with a solution of 1 part of Calgon. (sodium hexa-meta-phosphate) and 1 part of the poly-- condensate of ethylene oxide with mixed amyl phenolsin 1000 parts of water, rinsed and dried. Following scouring the fabric was rinsed well with water and then. dried. The cellulose acetate fabric was dyed a greenishblue shade having excellent fastness to washing and light..

EXAMPLE 8 A cellulose acetate tricot fabric was dyed using an aqueous dye bath prepared by using 2% by weight off a dye mixture containing 40% by weight of the blue dyel,8 dihydroxy 4-(mu-methylrnethylolanilino)-5-nitroanthraquinone and 60% by weight of sodium lignin sulfonate. After drying, the dyed material was padded witlr a 2% solution of ferric thiocyanate in such a manner that a pickup of 60-l00% (based on the weight of the fabric) was obtained. After ageing and finishing as in Example 1, a washand light-fast blue dyeing, slightly duller and greener than the original non-metallized dyeing, was obtained.

Substantially the same results are obtained if a 2% aqueous solution of ferrous thiocyanate is used in place of ferric thiocyanate in the foregoing example.

EXAMPLE 9 Example 4 was repeated using an equal quantity of the blue dye 1,8-dihydroxy-4-(p-toluidino)-5-nitroanthraquinone in place of the blue dye 1,8-dihydroxy-4- (p- ,B-hydroxyethylanilino)-5-nitroanthraquinone. A beautiful greenish-blue print having excellent fastness properties on a white ground was obtained.

EXAMPLE 10 1.88 grams of 1,8-dihydroxy-S-nitro-4-anilinoanthraquinone was refluxed in 30 cc. of acetone. 4 cc. of 28% aqueous ammonium hydroxide were added through the condenser followed by the addition of a solution of 1.37 grams of nickelous acetate (Ni[OOCCH .4H O) in 30 cc. of hot 50% aqueous acetone. Following these additions the reaction mixture resulting was stirred at the boil for 2.5 hours and then drowned in 800 cc. of water. The metallized dye compound formed was recovered by filtration and washed with hot water until the filtrate comes through colorless. After drying under vacuum at 60 C., 2.42 grams of the nickel complex of 1,8-dihydroxy-S-nitro-4-anilinoanthraquinone was recovered as a dark blue powder.

EXAMPLE 11 1.75 grams of 1,8-dihydroxy-4-(m-methylolanilino)-5- nitroanthraquinone, 4 cc. of 28% aqueous ammonium hydroxide, 30 cc. of, ethyl alcohol and a solution of 1.5 grams of cobaltous chloride crystals in 15 cc. of water were refluxed for 6 hours with good stirring. .After refluxing, the reaction mixture was drowned in 750 cc. of hot water and then filtered. The metallized (dye recovered on the filter was washed with hot water until the filtrate comes through colorless. After drying 1.94 grams of the cobalt complex of 1,8-dihydroxy-4- (m-methylolanilino)-5-nitroanthraquinone were obtained :as a dark blue pigment.

EXAMPLE 12 10 grams of yarn type cellulose acetate in 56 grams aof acetone, 25 grams of coarse sand and 0.2 gram of the metallized dye product of Example 10 were ground together until the average particle size of the dye pigment was 1 to 2 microns as determined microscopically. The sand was filtered 01f by passing the mixture through a fine sieve. Upon casting the filtrate into a film or extruding it in yarn form in the usual manner a beautiful greenish-blue yarn which has good fastness to light and washing is obtained.

EXAMPLE 13 1.95 grams of =1,S-dihydroxy-5-nitro-4-p-toluidinoanthraquinone was refluxed in 30 cc. of acetone. 4 cc.

of 28% aqueous ammonium hydroxide were added through the condenser followed by the addition of a solution of 1.37 grams of nickelous acetate (Ni[OOCCH .4H O) EXAMPLE 14 10. grams of yarn type cellulose acetate in 56 grams of acetone, 25 grams of coarse sand and 0.2 gram of the metallized dye product of Example 13 are ground together until the average particle size of the dye pigment was 1 to 2 microns. as determined microscopically. The sand was filtered ofi? by passing the mixture through a fine sieve. Upon casting the filtrate into a film or extruding it in yard form in the usual manner a beautiful greenish-blue yarn which has good fastness to light and washing is obtained.

EXAMPLE 15 A 3% dyeing on a cellulose acetate textile fabric of the dye 1,5-dihydroxy-8-nitro-4-m-hydroxymethylanilinoanthraquinone was padded with a 3% aqueous solution of nickel thiocyanate so that the pickup was 60l00% based on the weight of the dyed fabric. The padded fabric was then steamed for -10 minutes at p.s.i. in a steam chest, rinsed with water, scoured at 60 C. with a 0.5% soap and 0.5% soda solution in water for 20 minutes, rinsed with warm water and airdried. The deep blue dyeing thus obtained withstands a standard AATCC No. 3 wash test Without bleeding or staining.

EXAMPLE 16 1.88 grams of 1,S-dihydroxy-S-nitro-4-anilinoanthraquinone dissolved in 30 cc. of methyl Cellosolve were heated on a steam bath. 4 cc. of 28% aqueous ammonium hydroxide were added followed by the addition of a solution of 1.37 grams of nickelous acetate (Ni[OOCCH .4H O) in 30 cc. of hot 50% aqueous methyl Cellosolve. The reaction mixture resulting was heated, with stirring, at the boil for 8 hours and then drowned in 800 cc. of cold water. The metallized anthraquinone dye compound formed was recovered by filtration, washed with hot water until the filtrate came through colorless and dried. When the metallized anthraquinone dyestufi is finely ground and intimately dispersed in a cellulose acetate-acetone dope and the dope is extruded into yarn or cast into film in the usual manner deep blue shades having excellent resistance to the action of light, gas and laundering, for example, are obtained.

EXAMPLE 17 Example 15 was repeated using the dye 1,5-dihydroxy- 8-nitro-4-p-;3-hydroxyethylanilinoanthraquinone in place of the dye 1,S-dihydroxy-8-nitro-4-m-hydroxymethylanilinoanthraquinone. The cellulose acetate fabric was dyed a blue shade having excellent fastness to washing and light, for example.

EXAMPLE 18 Example 16 was repeated using 1.91 grams of 1,5- dihydroxy-8-nitro-4-p-toluidinoantl1raquinone in place of 1.88 grams of 1,5-dihydroxy-8-nitro-4-anilinoanthraquinone and 1.38 grams of cobaltous acetate in place of 1.37 grams of nickelous acetate. Beautiful blue articles having excellent resistance to the action of light, gas and laundering, for example, were obtained.

EXAMPLE 19 Example 15 was repeated using the dye 1,5-dihydroxy- 8 nitro 4 m a methylmethylolanilinoanthraquinone in place of the dye l,5-dihydroxy-8-nitro-4-m-hydroxymethylanilinoanthraquinone and a 3% aqueous solution of cobalt thiocyanate in place of a 3% aqueous solution of nickel thiocyanate. The cellulose acetate fabric was dyed a blue shade having excellent fastness, for example, to light, gas, laundering and sublimation.

EXAMPLE 20 3 parts of a dye mixture containing 40% by weight of the blue dye 1,S-dihydroxy-8-nitro-4-p-methoxyanilinoanthraquinone and 60% by weight of sodium lig nin sulfonate were pasted with 5 parts of hot water and 6 parts of'di-B-hydroxyethyl sulfide. 30 parts of a 3% aqueous nickel chloride solution also containing 8 grams of ammonium thiocyanate were stirred in and the resulting mixture was then mixed with 55 parts of an 8% aqueous gum tragacanth solution until a homogeneous dispersion was obtained. A cellulose acetate bark-cloth was printed, through a screen, with the printing paste, prepared as just described, using three squeegee passes. The print resulting was dried and then aged for 30 minutes in a steam chest at 10 p.s.i. The print was then scoured at C. in an aqueous solution of 1% of Triton 720 (a polyethylene oxide condensate of an alkyl phenol) and 0.5% sodium carbonate. After the scouring treatment, the print was rinsed well with water and then dried. The result was a bright greenish-blue pattern on a white background. No bleeding or change in depth of color was noticed afted a standard AATCC No. 3 wash test.

EXAMPLE 21 EXAMPLE 22 2.2 grams of the dye 1,5-dihydroxy-8-nitro-4-m-ethoxyanilinoanthraquinone, 20 cc. of formamide and 2 grams of CrCl were heated together, with stirring, at -130 C. for six hours. The resulting solution was poured into 500 cc. of cold water and the metallized anthraquinone dye compound which precipitated was recovered by filtration, washed well with hot water and dried. When the metallized anthraquinone dyestulf thus obtained is finely ground and intimately dispersed in a cellulose acetate-acetone dope and the dope is extruded into yarn in the usual manner blue filaments having excellent fastne ss to light and Washing, for example, are obtained.

EXAMPLE 23 Example 20 was repeated except that the metallizing agent used was copper tartrate instead of nickel chloride. Blue prints of excellent wash fastness, for example, were obtained.

It will be understood that the foregoing examples are illustrative and not limitative of our invention. Thus 1,8 dihydroxy 4 (0 8 hydroxyethylanilino) 5- nitroanthraquinone, 1,8 dihydroxy 4 (p ,3 hydroxypropylanilino) 5 nitroanthraquinone, 1,8 dihydroxy 4 (p 'y hydroxypropylanilino) 5 nitroanthraquinone, 1,8 dihydroxy 4 (p 13 hydroxyethoxyethoxyanilino) 5 nitroanthraquinone, 1,8 dihydroxy 4 (m ,8 methoxyethoxyanilino) 5 nitroanthraquinone, 1,8 dihydroxy 4 (p )3 ethoxyethoxyanilino) 5 nitroanthraquinone, 1,5 dihydroxy- 4 (p B hydroxypropylanilino) 8 nitroanthraquinone, 1,5 dihydroxy 4 (o [3, dihydroxypropylanilino) 8 nitroanthraquinone, 1,5 dihydroxy 4 (p- 18 hydroxyethoxyethoxyaniliuo) 8 nitroanthraquinone and 1,5 dihydroxy 4 (p B ethoxyethoxyani1ino)- 8 nitroanthraquinone, for example, can also be used in preparing metallized anthraquinone compounds of our invention in accordance with the procedures described in Examples 1 to 23.

'Similarly other metallizing agents than those specifically disclosed in Examples 1 to 23 can be employed. To illustrate, by the use of manganese chloride and vanadium tribromide, respectively, in place of cobalt thiocyanate in Example 1, for example, the manganese and the vanadium complex, respectively, of 1,8-dihydroxy 4 (p B hydroxyethylanilino) 5 nitr'oanthra- Preparation of acylonitrile graft polymer 3.0 g. of acrylonitrile and 7.0 g. of N-methyl methacrylamide were emulsified in 40 cc. of water containing 0.15 g. of potassium persulfate and 0.01 g. of tertiary dodecyl mercaptan. The emulsion was heated at 60 C. until 94% or more of the monomers had copolymerized. This result is usually accomplished by heating for about 12 hours. The copolymer contained approximately 30% by weight of acrylonitrile and 70% by weight of N-methyl methacrylamide. The mixture was then cooled to room temperature, 50 cc. of water added and the mixture agitated until a homogeneous solution of dope containing by weight of the copolymer resulted.

30.7 g. (3.07 g. of copolymer) of the above prepared solution or dope of the copolymer were placed in a jacketed reactor provided with an agitator and heat exchanger. There were then added 10 g. of acrylonitrile, 114 cc. of water, 0.58 g. of 85% phosphoric acid, 0.1 g. of potassium persulfate, 0.17 g. of potassium metabisulfite, 0.1 g. of tertiary dodecyl mercaptan and 0.56 g. of a 30% solution in water of N-methyl methacrylamide and the mixture heated, with stirring, to 35 C. and then allowed to level off at 3739 C. After the heat of polymerization had been removed and when the conversion of the acrylonitrile to polymer had reached 96% or more, which is usually accomplished in a period of about 12 hours, the temperature was raised to 90 C. The mother liquor was removed by centrifuging the polymerization mixture, the polymer precipitate being reslurried twice with water and centrifuged to a 70% moisture cake. The cake was dried under vacuum at 80 C. in an agitated dryer. The overall yield of modified polyacrylonitrile product was over 90%. After hammer-milling, the dry powder, now ready for spinning, was stored in a moisture pro-of container.

The acrylonitrile graft polymer prepared as above and containing about 18% by weight of N-methyl methacrylamide was soluble in N,N-dimethylformamide. Fibers spun by extruding a solution of the polymer product in N,N-dimethylformamide into a precipitating bath had a softening temperature of about 240 C., an extensibility of about 20-30 percent depending on the drafting and relaxing conditions, and showed excellent afiinity for dyes.

The non-metallized anthraquinone dye compounds having the Formulas II and III can be applied to cellulose alkyl carboxylic acid esters having 2 to 4 carbon atoms in the acid groups thereof, nylon, an acrylonitrile polymer, such as polyacrylonitrile and acrylonitrile graft polymers, and polyester, such as polyethylene terephthalate, textile materials and the metallized anthraquinone dye compounds of our invention can be applied to nitrogenous textile materials such as, for example, wool, silk, nylon and acrylonitrile polymers, such as polyacrylonitrile and acrylonitrile graft polymers, in the form of an aqueous dispersion and are ordinarily so applied.

To illustrate, the dye compound is finely ground with a dispersing agent such as sodium lignin sulfonate, Turkey red oil, soap, or an oleyl glyceryl sulfate and disease? the-resulting mixture is dispersed in water. The dye bath thus prepared is heated to a temperature approximating 45 C.55 C. and the textile material to be dyed is immersed in the dye bath, following which the temperature is gradually raised to C.- C. and maintained at this temperature until dyeing is complete, usually one-half to two hours. From time to time throughout the dyeing operation, the material is worked to promote even dyeing. Upon completion of the dyeing operation, the textile material is removed from the dye bath, washed with an aqueous soap solution, rinsed well with water and dried. In the case of certain of the acrylonitrile graft polymers described hereinbefore it is necessary to dye at the boil for an extended period of time. Instances may be encountered where the fiber is not satisfactorily colored by the dyeing procedure just described. In these instances special dyeing techniques, such as the use of pressure, for example, developed by the art for the coloration of each difficultly colored materials may be employed.

Widely varying amounts of dye can be used in the dyeing operation. The amount of dye used can be, for example, /3 to 3% (by weight) of that of the textile material although lesser or greater amounts of the dye can be employed.

The following example illustrates one satisfactory way in which the fibers of the acrylonitrile graft polymers can be dyed using either the metallized anthraquinone compounds of our invention or the non-metallized anthraquinone compounds having the formulas numbered II and III. 16 milligrams of dye are ground with an aqueous solution of sodium lignin sulfonate until Well dispersed or alternately the dye can be dissolved in 5 cc. of hot Cellosolve. The dispersion or solution, as the case may be, is then poured into cc. of water to which a small amount of a surface-active agent such as Igepon T (C H .CO.N(CH ).C H SO Na) Nekal BX (sodium alkylnaphthalenesulfonate) or Orvus (sodium lauryl sulfate-type) has been added. The dye bath is then brought to the desired temperature and 5 grams of well Wet-out fibers of the graft polymer are added thereto. Dyeing is continued until the proper shade is reached. From time to time throughout the dyeing operation, the material is worked to promote even dyeing.

The metallized anthraquinone dye compounds of our invention color nylon and acrylonitrile polymers slightly greener shades than they color cellulose acetate.

Acrylonitrile graft polymers including those of the type specifically described hereinbefore are described and claimed in Coover U.S. application Serial No. 408,012,

filed February 3, 1954, and now U.S. Patent No.

This application is a continuation-in-part of our application Serial No. 446,954,, filed July 30, 1954, and now abandoned.

We claim:

1. A complex metal compound which contains a metal selected from the group consisting of chromium, cobalt, copper, iron, manganese, nickel and vanadium in complex combination with an anthraquinone compound having the formula:

Y it

wherein R represents a monocyclic aryl nucleus of the benzene series and X and Y each represent a different member selected from the group consisting of a hydroxy group and a nitro group.

2. A complex metal compound which contains a metal 11 selected from the group consisting of chromium, cobalt, copper, iron, manganese, nickel and vanadium in complex combination with an anthraquinone compound having the formula:

no on C ON ii NR wherein R represents a monocyclic aryl nucleus of the benzene series.

3. A complex metal compound which contains a metal selected from the group consisting of chromium, cobalt, copper, iron, manganese, nickel and vanadium in complex combination with an anthraquinone compound having the formula:

0,N (I 0H 7 wherein R represents a monocyclic aryl nucleus of the benzene series.

4. Complex nickel compounds of the anthraquinone compounds having the formula:

HO O OH 1] 021 1 O N-R wherein R represents a monocyclic aryl nucleus of the benzene series.

5. Complex cobalt compounds of the anthraquinone compounds having the formula:

OzN d N-R wherein R represents a monocyclic aryl nucleus of the benzene series. 6. Complex nickel compounds of the anthraquinone compounds having the formula:

OnN (H) OH i H0 0 N-R 12 wherein R represents a monocyclic aryl nucleus of the benzene series.

8. A complex metal compound which contains a metal selected from the group consisting of chromium, cobalt, copper, iron, manganese, nickel and vanadium in complex combination with an anthraquinone compound having the formula:

wherein X and Y each represent a different member selected from the group consisting of a hydroxy group and a nitro group and Z represents a member selected from the group consisting of a hydrogen atom, a methyl group, a methylol group, an a-methylmethylol group, a ,B-hydroxyethyl group, a fi-hydroxypropyl group, a 'y-hydroxypropyl group, a p,'y-dihydroxypropyl group, a B-hydroxyethoxy group, a fl-hydroxy-p-ethoxyethoxy group, a p-hydroxy-B-ethoxy-p-ethoxyethoxy group, a fl-methoxyethoxy group, a fi-methoxy ,B-ethoxyethoxy group, a fl-ethoxyethoxy group and a p-ethoxy-fl-ethoxyethoxy group.

9. A complex metal compound which contains a metal selected from the group consisting of chromium, cobalt, copper, iron, manganese, nickel and vanadium in complex combination with an anthraquinone compound having the formula:

X E (I111 @011 II I Y 0 II O N -R H OgN wherein R represents a monocyclic aryl nucleus of the benzene series containing as the sole substituent a monohydroxyalkyl group having 1 to 3 carbon atoms.

11. Complex cobalt compounds of the anthraquinone compounds having the formula:

rN fl) OH C 1 HO 6 N-R wherein R represents a monocyclic aryl nucleus of the benzene series containing as the sole substituent a monohydroxyalkyl group having 1 to 3 carbon atoms.

12. Acomplex nickel compound of the anthraquinone compound having the formula:

17. A complex nickelcompound of the anthraquinone compound having the formula:

OnN O OH l/gn H &6

18. A complex nickel compound of the anthraquinone compound having the formula:

13. A complex nickel compound of the anthraquinone compound having the formula:

no 0 on on: 0 on I g g o o OgN 8 0011: n A g-O-omornon 19. A complex nickel compound of the anthraquinone compound having the formula:

OzN OH HaQH 20. A complex nickel compound of the anthraquinone compound having the formula:

14. A complex nickel compound of the anthraquinone compound having the formula:

15. A complex nickel compound of the anthraquinone compound having the formula:

16. A complex nickel compound of the anthraquinone HoH compound having the formula:

no 0 on a No references c1ted.

HOE 

1. A COMPLEX METAL COMPOUND WHICH CONTAINS A METAL SELECTED FROM THE GROUP CONSISTING OF CHROMIUM, COBALT, COPPER, IRON, MANGANESE, NICKEL AND VANADIUM IN COMPLEX COMBINATION WITH AN ANTHRAQUINONE COMPOUND HAVING THE FORMULA: 